Anthraquinone derivative and process of making same.



' eesgzee He mowing. Apolication filed February 25, 1916, Serial lie-80,395. Renewed. 5 :13 3513, 283.5. Sc

HEGIEG- WESGHEB, 0F e 4- slli'ii I R, NEAR BRAIN KFOBT-ON -TEE-1YLAIfi-i 5 Pateni-ed Fimkfort-on-the-Mein, Germany, have invented e oerteio New Anthmquinone Derivolive end Process of Making Same, of which the following is a full description.

1 have disoovemd that when heating lamino-2-methylenihrequinone with aromatic nitro compounds in presence of elkalis to eie'mied tempei'atures, intensely colored products of eondensetion are obtained. The reaction sakes place While water is split ofi, probably in such a manner that the methyl group oi the lemino-Q-methylantraquinone is oxidized by the nitro compound used; at the time a, condensation of the two molecules takes plaoe. Perfectly analogous compounds are obtained if the reaction is carried out in the presence of primary aromatic 21mins. In this case the used niti'o compound acts as an oxidizing agent, Whereas the used amine immediately form condensation products with the l-amino-Q-methylentliraqninone oxidized by the nitro compound; these condensation products, according to their behavior, possess a constitution illlSOlll'fiBljf analogous to that of the condensation products. produced by means of liiiiO compounds alone. Conseqiiently when using the emin corresponding to the nit-ro compound used the same compound is obtained as when using the nitro compound alone.

} have fort-her discovered that the condom setion oi'oduots thus obtained are split by the reaction oi acids, and that they one and ell yield the some derivative of enthi'equinone, which accordio to its properties and according to tile resuit of the analysis, musibe considered as l-aminoanthrequinoneQ-aldeliyde, of the following formula,

As besides ion of those of the nitro compounds ased} sis compound, only the forms-- may be proved which have the T0llli3l03l of the respeeiive of condensation, it must be presumed t these products of condensation are azome' thin compounds of the following forznole (where R i'epreseaiiis any .aron" The process oi Working; the following examples:

Examplel: To a, solution amino-Q-metliylenthraquiiione 1 5G es nitrobenzene o kilos carbonate of e added and the mixture is kept boiling for hours. idle intense bluish red solution, when filtered host, the new garoduct of condensation separates on cooling. Pay CIT/5S- tallizing from nitrobenzene is obfieined if; brilliant red crystals with e melting point of 212 C. The compound "ssolves in on genie solvents of e high be poin Wits a bluish red color. 5

whole mixture is boiled for 6 hours. The solution is filtered hot, and on cooling same, a compound separates in brilliant red crystals which, as is confirmed by its reactions and the melting point, is identical with the compound obtained when working accordin to Example 1. The same compound results if the carbonate of potash used is substituted by 1 kilo caustic soda.

. Example l: 10 kilos 1-amino-2-methylanthraquinone, S kilos betanaphthylamin, 5 kilos carbonate o'l' potash and (30 kilos nitrobenzene are heated for (3 hours to about 22?)" (I. (exterior temperature). ()n cooling the hotly filtered SOllltlOIl,l-ll new compound separated is'liltered off after cooling. The

corre ponding quantity of anilin'is to be found in the filtrate. By crystallization from nitrobcimnw, the l-aminoanthraquinono-2-aldehyde is obtained in the form of cl' \';-;tuls with a metallic luster, melting at about .2 l It is very diflicultly soluble in alcohol, soluble in organic solvents of. a high boiling point. It dissolves in concentrated sailt'uric acid with a brown color which I on addition of paraformaldehyde is changed lI]'lT1'l(?(ll2ll.Ql Y into an intense blue. With hydrosullite and caustic soda lye a bri ht green vat is lornu-d which dyes cotton int very slightly.

l'lxample 3: l0 kilos of the product of condensation obtained when WOIkll'l according to Example 4 are dissolved at at out 30 (3. in 100 kilos concentrated sulfuricacid. 20 kilos water are then added radually to the orange red solution, seeing t at the tempcratun-v docs notexcecd 90 C. After half an hour's sill-ring, the mixture of the reactio is poured into water wherebythe 1- a minoa m hraquinonc-2-aldebyde separates in lli'v shape f vcllowish red flakes which are isolatwl in the usual manner. The comound p rfectly corresponds in properties with the ('(iflllifllllld obtained when working ac ording to Example 5, whereas the correspending! quantity of hetanaphthylamin is in be found in'the filtrate.

liming now particularly described and ascertained lhc nature of my said invention, and in what manner the same is tolbe performed, I rlecla re that what I claim is:

l. The process of producing l-arninoanthraquinone-iZ-aldehyde of the following formula l l by treating with acids the products of'condvnsation of the general formula: a

(where ll re )rcsmits an v aromatic rou i D 3 (producin l-amjnoane of t e following k ra by treating with acids the products of condensation of the general formula:

(where R represents any aromatic group),

which are obtained by heating 1-amino-2- methylanthraquinone with aromatic nitro compounds with the addition of primary aromatic amins in the presence of alkalis, the 1-aminoanthraquinone-Q-aldehyde thus obtained cryslallizing in crystals with a metallic luster, melting at about 233 0., dissolving in concentrated sulfuric acid With a brown color, which on addition of para-- formaldehyde changes to an intense blue, yielding with hydrosulfite and caustic soda lye a bright green vat. substantially as described.

3. The herein described new -l-aniino anthrequinone-Q-aldehyde of the following formula:

10 crystallizing in crystals with a metallic luster, melting at about 233 6., d1ss0lving in concentrated sulfuric acid with a brown color, which on addition of Paraformaide hyde is changed into blue, yie ding with hy-' drosulfite and caustic soda lye a; bright 15 green vat, substantially as describeci In witness whereof I have hereunbo signed my name this 26th day of January, 1916, in

H the presence of two subscribing witnesses.

DB. GEORG KALISCHEB. Witnesses JEAN GBUND, HARRY E. Carson. 

